Derivatives of bis-(1-amino-anthraquinone-6-sulfo)-piperazid



UNITED STAT Patented Feb. 12, 1952 DERIVATIVES .l'oii BIs-(i-AMINmANTnRA- QUINONEfi-SURFO) -P IPERAZID Walter Jenny, Basel, and Walter Kern, Sissach, Switzerland, assignors to Ciba Limited, a Swiss 1N0 Drawing. Original applicationDe'cember 18, I

1947, Serial No. 792,616. Divided and this application January 25, 1951, Serial No. 207,833. In Switzerland December 21, 1946 I PATENT OFFICE 4 Claims, to]. 260-268) .This application is a division ofour copending application Serial No. 792,616, filed on December 18, 1947 (now U. S. Patent, No. 2,553,411).

Under the present invention, valuable vat dyestufis are made by converting in an anthraa sulfochloride group in fi-position. The transformation of such a sulfonic acid group into a sulfonic acid amide group can be effected conveniently by first transforming a sulfonic acid group into a reactive derivative thereof, if such a reactive derivative is not present rightfrom the beginning. The reaction between sulfonic acid halides, especially sulfochlorides, with ammonia or primary or secondary amines may be carried out as a rule at comparatively low temperature, if desired, with gentle warming.- Depending on' the amines'used an excess thereof may be used as solvent or the reaction may be In many instances especially good results are'obtained if the said sulfonic acids or the sulfonic acid halide groups are transformed into sulfonic acid amide groups which carry 2 alkyl radicals attached to the nitrogen atom. This can be effected easily by reacting the sulfonic acid halides with secondary aliphatic amines, for example, dimethylamine, diethylamine, or diethanolamine. In' some cases it is also possible to alkylate the sulfonic acid amides which are first formed and which do not carry an alkyl group at the nitrogen atom or contain at most one such alkyl group, whereby the corresponding N -dialkylsulfamides are obtained. In the dialkylsulfaniides mentioned above both alkyl groups may be completely separated ,fromeach other or they may be in- 'terconnectedto form an isocyclic or hetero'cyclic ring. Thus, for example, by reacting sulfochlorides with piperidine, s'ulfopipe'ridides. for: by're- 30' carried out in an indifferent diluent or solvent.

acting sulfochloride with morpholine, sulfomorpholides, are obtained.

For the transformation of sulfonic acid groups into sulfonic acid amide groups one may also use amines which carrymore than 1, for example 2,

amino groups which are interconnected for instance by an aliphatic radical or may form part of a heterocyclic ring, for example, a piperazine ring.

-' Besides the transformation of sulfonic acid groups into sulfonic acid amide groups as described above the present process comprises a reaction which consistsin transforming a suitable substituent in the anthraquinone nucleus into a carboxylic acid amide group in such a manner that its nitrogen atom is directly bound to the anthraquinone radical. Substituents suitable for such transformation are of course amino groups .which can be acylated in the usual manner. As

the presence of free amino groups might interfere with the transformation of sulfonic acid groups into sulfonic acid amide groups described above it is oftenv necessary to carry out the sec- 5 -ond mentioned reaction in a round-about way.

In the vattable starting product the amino group may not be-present or it may be present in such a form that a disturbing side-reaction cannot occur. Forin'stance, the starting product may contain-besides the sulfonic acid group to be transformed into a sulfonic acid amide group, a nitro group which ata given moment may be reduced to an amino group and may subsequently be acylated. As an alternative, the starting product may contain a replaceable halogen atom which 'at a suitable moment is replaced by an amino group, or such a replaceable halogen atom may be reacted with a carboxylic acid amide to form the corresponding .carboxylic acid amide group, the nitrogen atom of which is directly attached to a vattable radical.

The two reactions necessary for. the present process, viz. the transformation of the sulfonic acid group (or its reactive derivative) into a sulfonic acid amide group and the introduction of an acylamino group into an anthraquinone radical. may be carried out in anydesired sequence.

in many cases, it willbe convenient first to carry out the first mentioned reaction, thereafter reducingia'nitro group 'initially present in, or subsequently introduced into, the molecule to an amino group and to acylate the latter.

The carboxylic acids or the functional derivatives thereof (especially halides) intended for the acylation of amino groups may belong to the aliphatic, aromatic or heterocylic series. Especially good results are obtained in many instances by using aromatic carboxylic acids, such as benzoic acid or substituted benzoic acids, for example alkyl, halogen or cyanbenzoic acids, wherein often a p-positioned substituent is preferable. If desired, polyvalent carboxylic acid, for example, benzenedicarboxylic acids such as terephthalic acid and isophthalic acid may be reacted with vattable compounds of the kind described above in such a manner that each carboxylic group of the acid used leads to the formation of a carboxylic acid amide group. The reaction of the carboxylic acids used with the amines of vattable compounds may be carried out by using the corresponding acid chloride at an elevated temperature in high boiling solvents or diluents such as mono-, dior trichlorobenzene, nitrobenzene or naphthalene.

Especially valuable products may be obtained according to the process by converting nitroanthraquinone-sulfonic acids whose nitro group is bound, for example, to a l-position and whose sulfonic acid group is bound to one of the positions 6 and 7, i. e. in the benzene nucleus of the anthraquinone not containing the nitro group, into the corresponding sulfonamides. The nitro group is then reduced and the amino group thus obtained is acylated.

The products obtained according to the present process are vat dyestufis which carry as substituents in ii-position in an anthraquinone nucleus at least one sulfonic acid amide group and furthermore at least one carboxylic acid amide group, the nitrogen atom of which is directly attached to the anthraquinone radical. In these vat dyestufis the sulfonic acid amide groups may carry advantageously two alkyl radicals bound to the nitrogen atom and these alkyl radicals may be interconnected to form a ring.

The present products may be used in known manner for dyeing and printing various fibers, especially cellulosic fibers, and also as pigments. There are obtained, inter alia, for example, violet, and also valuable, pure yellow shades of good fastness.

The following examples illustrate the invention without limiting its scope. The parts are parts by weight unless otherwise stated.

Example 1 To a solution of 1-nitro-anthraquinone-fi-sulfochloride (1 molecular proportion) [obtainable by reacting phosphorus pentachloride and pliesph'orus oxychloride with sodium l-nitroanthraquinone-G-sulfonate] in acetone, 2 molecular proportions of dimethyl amine are added slowly with good stirring at -5 C. After the whole has been kept for 3 hours while stirring at 40 C. the mixture is cooled down, filtered and washed well with warm water, alcohol and ether. The product obtained forms, when recrystallized from benzene, pale yellow needles or laminae melting at 271-2'72 C. (uncorrected). By reduction by. means of an aqueous sodium sulfohydrate solution l-aminoanthraquinone 6 sulfodimethylamide is obtained which, after recrystallization from chlorobenzene, forms beautiful red crystals melting at 237-239 C. (uncorrected).

17 parts of l-amino-anthraquinone-6-sulfodimethylamide thus obtained are suspended in 900 parts of dry chlorobenzene, 30 parts of para-chlorobenzoylchloride added and the whole is boiled for 3 hours with reflux cooling. The dyestufi, which on cooling crystallizes to form yellow needles, is suction-filtered and well washed with hot alcohol. It corresponds to the formula 0 NHC 00-01 NSO2 C a g and dyes cotton from a red-brown vat in pure greenish yellow shades.

The reaction may also be carried out-in other solvents such as ortho-dichlorobenzene, trichlorobenzene or nitrobenzene.

Example 2 22 parts of l-amino-anthraquinone-S-sulfodimethylamide (see Example 1, paragraph 1) are suspended in 1000 parts of dry chlorobenzene and '1 parts of terephthalic acid dichloride are added. The whole is kept gently boiling for 3 hours. The dyestuff, which on cooling separates in yellow needles, is suction-filtered and well washed with boiling alcohol. It corresponds to the formula CHi S Oa--N (JHa and dyes cotton from a dark brown vat in strong, pure yellow shades with good fastness properties.

The reaction may alternatively be carried out in other solvents such as ortho-dichlorobenzene, trichlorobenzene or nitrobenzene.

If isophthalic acid dichloride is used instead of terephthalic dichloride a dyestuif of similar properties is obtained.

Example 3 88 parts of the oxaminic acid of l-amlnoanthraquinone-6-sulf0dimethylamide (see Example 1, first paragraph) obtained according to the usual methods, are dissolved at 0-5 C. in 880 parts of concentrated sulfuric acid. To this solu tion a mixture of 30 parts of nitric acid of 63% strength and 60 parts of concentrated sulfuric acid are slowly added while stirring at the same temperature. After stirring for a further two hours at 0-5" G. the reaction mixture is poured into 4000 parts of cold water. The precipitate is filtered, and washed with water until free from acid and stirred for 2 hours in a dilute sodium carbonate solution at 90-95 C. After filtering and washing until neutral a red compound is obtained which is easily reduced in a hot aqueous sulfohydrate solution to the diamino compound. The 1:4 diaminoanthraquinone 6 sulfodimethylamlde thus obtained forms, after recrystallisation from chlorobenzene, dark violet 'crys tals of metallic lustre, melting unsharply at 260 C.

285 parts of l:4-diaminoanthraquinone-fiesulfodimethylamide are dispersed in 2500 parts of dry nitrobenzene. After the addition of 500 parts of benzoylchloride the whole is stirred at 130-135 C. for 3 hours. The dyestuff, which precipitates in the form of red needles while the reaction mass is still hot, is suction-filtered when it has cooled down and well washed with hot alcohol. It dyes cotton from an olive vat pure reddish violet shades of good fastness.

NH-CO-O-OO-HN o CHn-C Hz N-S 0 CHz-C g The reaction may alternatively be carried out in other solvents, such as chlorobenzene, orthodichlorobenzene or trichlorobenzene.

Example 4 1 aminoanthraquinone 6 sulfopiperidide is made according to the method described in the first paragraph of Example 1, from l-nitroanthraquinone6-sulfoohloride and piperidine and subsequent reduction of the nitro-group [l 'nitroanthraquinone-G-sulfopiperidide forms, after GHQ-CH2 CH: N-SOz CHz-CHz I and dyes cotton from an olive brown vat very pure, strong greenish yellow shades with good fastness.

The reaction may alternatively be carried out in other solvents such as nitrobenzene, ortho-dichlorobenzene or trichlorobenzene.

Example 5 25.5 parts of l-aminoanthraquinone-6-sulfopiperidide (see Example 4, first paragraph) are dispersed in 280 parts of dry nitrobenzene, 12 parts of para-cyanbenxoylchloride are added and the whole is stirred for 3 hours at 90-100 C. After cooling the dyestufi which has separated is suction-filtered and washed with hot alcohol. It dyes cotton from an olive brown vat pure green ish yellow shades.

The reaction may alternatively becarried out in other solvents such as clilorobenzene,' ortho-dichlorobenzene or trichlorobenzene. 1

Example 6 37.2 parts of 1-aminoanthraquinone-G-sulfo- CHI-C32 -S 02- O If isophthalic acid dichloride is used a dyestufi is obtained which .dyes somewhat less powerful shades.

1-aminoeanthraquinone-6-sulfomorpholide may be obtained in the same manner as the corresponding sulfopiperidide (Example 4). It forms on recrystallation from chlorobenzene red needles.

Example 7 23 parts of 4-benzoyl-benzoic acid are dispersed in 500 parts of dry nitrobenzene and after the addition of 15 parts of thionylchloride and a asmall quantity of pyridine the mixture is stirred for 1 hours at 80-90 C. 37 parts of l-aminoanthraquinone-fi-sulfomorpholide are then added and stirring is continued for 2 more hours at 120- 130 C. On cooling the dyestufi separates in the form of yellow needles. It is suction-filtered, washed with boiling alcohol and dried. The dyestufl thus obtained is dissolved in concentrated sulfuric acid with a yellow coloration and dyes cotton from a black violet vat in pure greenish yellow shades with good fastness properties.

If instead of 1-amino-anthraquinone-6sulfomorpholide other amines, such as l-amino-anthraquinone-B-suIfopiperidide, l-amino-anthraquinone-6-sulfodimethylamide, or l-amino-anthraquinone-fi-sulfomethylanilide are used, similar dyestufis are obtained.

Example 8 26 parts of 1:4-diamino-anthraquinone-6-su1- fopiperidide are dispersed in 350 parts of dry nitrobenzene, parts of benzoylchloride are added, and the whole is stirred for 3 hours at 130-135 C. After cooling down, the dyestufi which has separated in the form of dark red needles is suctionfiltered, washed with hot chlorobenzene and boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a yellow coloration and dyes cotton from an olive vat red shades which become much bluer on soaping,

If the acylation is carried out with ll-methylsulfonebenzoic acid a similar dyestuff is obtained.

1:4-diamino-anthraquinone- 6 -suliopiperidide may alternatively be prepared according to the method given in Example 3 for the preparation of 1:4 diamino-anthraquinone-fi-sulfodimethylamide.

Example 9 nltrobenzene and 10.1 parts of terephthalic acid the addition of parts of thionylchloride and a dichloride are added and the whole is stirred for small quantity of pyridine the Whole is stirred at '3 hours at 125-l35 C. The dyestuff which sepa- 90-100 C. for 1 /2 hours. 37 parts of l-aminorates on cooling as a yellow powder, is suctionanthraquinone-B-sulfopiperidide are then added filtered, well washed with boiling alcohol and 5 and stirring is continued for 2 more hours at dried. It dissolves in concentrated sulfuric acid 120-130 C. The dyestuff which separates on with yellow-orange coloration and dyes cotton cooling in the form of yellow needles is suctionfrom an olive-brown vat pure yellow shades of filtered, washed with boiling alcohol and dried. very good fastness. This .dyestutf corresponds to It dissolves in concentrated sulfuric acid with a the formula in yellow coloration and dyes cotton from a brown i e -G r B o-cures; g om-om-on If amino-anthraquinone sulfodiethanolamides red vat .g-reenish yellow shades. are acylated with an excess of acid halides (for Similar dyestuffs are obtained if l-aminoaninstance benzoylchloride or para-chlorobenzoylthraquinone-6sulfodimethylamide, 1-amino-an-, chloride), the two OH-groups are also est'erified. 't h-raqu'inone-6 sulfomethylanilide and l-aminol -amino-anthraquinone-G-sulfodiethanolamide anthraquinon'e-6-sulfomorpholide are acylated by may be prepared by a method which is analogous means of diph'enyli-carboxylic acid halides.

'to that by which 1 amino anthraquinone-fi-sulfodimethylamide (Example 1) is prepared; when Example 12 reorystallized from nitrob'enzene the compound 2 parts of the d t fi obtained according to forms red needles. Example 2 are slurried in 200 parts of water and Eivample 19 after the addition of 8 parts by volume of caustic 65 parts of bis-(l-amino-anthraquinone-6- w soda solution of 36 B. and 4 parts of sodium sulfo)-.piperazide are dispersed in 2000 parts of hydrosulfite are vatted at 50-60 C. This stock dry nitrobenzene and after the addition of 120 vat is added to a dyebath containing, in 3000 parts of benzoylchloride the whole is kept boilparts of Water. '7 parts y volume of caustic soda ing for 3 hours while stirring. The dyestuii, solution of 36 Be. and 4 parts of sodium hydrowhich separates in the form of yellow crystals sulfite. 100 parts of well wetted cotton are enwhile the reaction mass is still boiling, is .suctered at C. After 15 minutes, 60 parts of tion. filtered after cooling down, well Washed with sodium chloride are added. The temperature is nitrobenzene and boiling alcohol and dried. It raised to C. and dyeing is effected for 1 hour dissolves in concentrated sulfuric acid with ared at this temperature. The cotton is squeezed, coloration and dyes cotton from a red-brown vat 4o oxidized in the air, rinsed in cold water, acidified, powerful greenish yellow shades of very Igood rinsed again, and, if desired, soaped. It is dyed fastness. This dyestuif is represented by the inpowerful pure yellow shades.

formula It is obvious that while the preferred embodi- GHQ-41H: -S O1,-N'/ g GET-CH1 g If instead of 'benzoylchloride, para-chloroments of the present invention have been parbenzoylchloride is used, a similar dyestuff is obticularly described above, changes and alteratained which dyes cotton in somewhat more redtions may .be made without departing from the dish shades. spirit thereof. Thus, if desired, the sulfonic acid The bis-(l amino-anthraquinone --6 -sulfo')- amide groups may contain only one alkyl subpiperazide mentioned above may be obtained as stituent attached to the nitrogen atom or even follows: none, the said groups may occupy a e-position To a solution of 105.5 parts of 1-nitro-anthraof the benzene nucleus in the anthraquinone quinone-G-sulfochloride and 24 parts of pyridine :30 radical which carries an acylamino group, but in 3800 parts of acetone, a solution of 30 parts preferably not in 1 and 2-position relatively to of piperazine (44%) in '600 parts of acetone is each other. The acyl radical of the acylamino slowly added drop by drop while vigorously stirgroup or groups may be an aliphatic acyl radiring at room temperature. When this addition cal such as an acetyl, propionyl-valerianyl or is complete, stirring is continued fore hours at even higher aliphatic acyl radical, or a hetero- 35-40 C. After cooling the solution is suctioncyclic acyl radical, such as the radical of a pyrifiltered and the residue is washed with hot water dine carboxylic or quinoline 'carboxylic acid such and dried. The nitro groups may be easily reas described in our co-pending patent applicaduced by means of an aqueous sulfohydrate solution Ser. No. 786,546, filed November 17, 1947 tion. The diamine is difiicultly soluble in almost (now U. S.=Pa tent No. 2,506,023). Furthermore any solvent. where the relativeposition'of the sulfamide group Example 111 and the acylamino group is 1:6 in the above examples, a relative position of 1:7 may be chosen 20 parts of diphenyll-carhoxylic acid are #disinstead, or mixtures containing compounds with persed in 350 parts of dry nitroben'zene andafter :bothrelative positions.

What we claim is: I wherein X stands for a member selected from the 1. A vat dyestuff corresponding to the general group consisting of halogen and hydrogen. formula R-O 0-1 11 1f11o 0-R 011F032 s01N N-SO2 g CH3CH2 g wherein RCO- stands for the radical of a ben- 3. The vat dyestufi of the formula zene monocarboxylic acid.

SON -so2 g 0112-0112 2. A vat dyestufi corresponding to the general formula CHr-CH:

-SON N--SO2 GET-C z A 4. The vat dyestuff of the formula G r i I if Q- WALTER JENNY. WALTER KERN.

No references cited. 

1. A VAT DYESTUFF CORRESPONDING TO THE GENERAL FORMULA 